Nef-isocyanide-Perkow access to novel ketene dithioacetals

Novel ketene dithioacetals have been synthesized viathe condensation reaction of active methylene compounds with carbon disulfide in the presence of Et3N in MeCN at room temperature. Phosphorylated hydroxyketenimines, synthesized via the reaction of ethyl chloroglyoxalate, cyclohexyl isocyanide and triethyl phosphide, were used for trapping of theketene dithioacetals to afford the push-pull olefinic product [1]. The phosphorylated hydroxyketenimines were generated in situ from a Nef-isocyanides-Perkow cascade reaction [2]. Various aspects of these transformations will be presented and discussed.